Chirality at Solid Surfaces

A comprehensive introduction to the fundamental aspects of surface chirality, covering both chemical and physical consequences

Written by a leading expert in the field, Chirality at Solid Surfaces offers an introduction to the concept of chirality at surfaces, starting from the foundation of chirality in isolated molecules and bulk systems. Fundamental properties such as surface energy and surface stress are then linked to a universal systematization of surface structure and symmetry. The author includes key examples of surface chemistry and physics, such as the interplay between adsorbate and substrate chirality, amplification of chirality, chiral catalysis, and the influence of surface chirality upon optical and magnetic phenomena. The book also explores the chirality apparent in the electronic structure of graphene, topological insulators and half-metallic materials.

This important reference:

• Provides an introduction to the fundamental concept of chirality

• Contains discussions of the chemical and physical consequences of surface chirality, including magnetic, electronic and optical properties in addition to molecular properties

• Offers an account of the most current research needed to support growth in the field

Written for surface scientists, professionals in the field, academics, and students, Chirality at Solid Surfaces is an essential resource that contains an overview of the fundamentals of surface chirality and reviews both the chemical and physical consequences.

Auteur

Dr. Stephen J. Jenkins, leads the Surface Science group in the Department of Chemistry at Cambridge University, where he directs both experimental and computational research on the physical and chemical properties of metal surfaces. His broad interest in the complexities of intermolecular interactions at surfaces finds particular focus in the expression of chirality in two dimensions, and its implications for asymmetric chemistry. He has worked in surface science for the past twenty-five years, and has published over 140 papers on a variety of topics within that field.

Résumé
A comprehensive introduction to the fundamental aspects of surface chirality, covering both chemical and physical consequences

Written by a leading expert in the field, Chirality at Solid Surfaces offers an introduction to the concept of chirality at surfaces, starting from the foundation of chirality in isolated molecules and bulk systems. Fundamental properties such as surface energy and surface stress are then linked to a universal systematization of surface structure and symmetry. The author includes key examples of surface chemistry and physics, such as the interplay between adsorbate and substrate chirality, amplification of chirality, chiral catalysis, and the influence of surface chirality upon optical and magnetic phenomena. The book also explores the chirality apparent in the electronic structure of graphene, topological insulators and half-metallic materials.

This important reference:

• Provides an introduction to the fundamental concept of chirality
• Contains discussions of the chemical and physical consequences of surface chirality, including magnetic, electronic and optical properties in addition to molecular properties
• Offers an account of the most current research needed to support growth in the field
  Written for surface scientists, professionals in the field, academics, and students, Chirality at Solid Surfaces is an essential resource that contains an overview of the fundamentals of surface chirality and reviews both the chemical and physical consequences.

Contenu

Preface xiii

Acknowledgements xxiii

1 Fundamentals of Chirality 1

1.1 Point and Space Groups 2

1.2 Proper and Improper Symmetry 4

1.3 Chirality in Finitude and Infinity 5

1.3.1 Molecular Chirality 5

1.3.2 Crystalline Chirality 8

1.4 Routes to Surface Chirality 9

1.4.1 Surfaces of Intrinsically Chiral Crystals 9

1.4.2 Intrinsically Chiral Surfaces of Achiral Crystals 10

1.4.3 Chiral Modification of Achiral Surfaces 11

1.5 Diastereoisomerism Defined 14

1.6 Quantifying Chirality? 15

1.7 Enantiomeric Excess 17

1.8 Synthesis, Separation and Sensing 19

References 20

2 Surface Symmetry and Structure 21

2.1 Spherical Representation of Symmetry 21

2.2 Spherical Representation of Structure 24

2.3 Stereographic Projections: Flattening the Globe 27

2.4 Surfaces of the Face-Centred Cubic Structure 29

2.4.1 Reconciliation of Symmetry and Primary Structure 29

2.4.2 Secondary and Tertiary Structure 32

2.4.3 Commentary 34

2.5 Surfaces of the Body-Centred Cubic Structure 36

2.5.1 Reconciliation of Symmetry and Primary Structure 37

2.5.2 Secondary and Tertiary Structure 39

2.5.3 Commentary 40

2.6 Surfaces of the Hexagonal Close-Packed Structure 42

2.6.1 Symmetry 43

2.6.2 Primary Structure 48

2.6.3 Reconciliation of Symmetry and Primary Structure 52

2.6.4 Commentary 55

2.7 Surfaces of the Diamond Structure 56

2.7.1 Symmetry 56

2.7.2 Primary Structure 58

2.7.3 Reconciliation of Symmetry and Primary Structure 59

2.7.4 Commentary 62

References 63

3 Surface Energy and Surface Stress 65

3.1 Thermodynamic Definition of Surface Energy 65

3.2 The Tensor Nature of Surface Stress 70

3.3 Visualisations of Surface Stress: Iconic Conics 71

3.3.1 The Normal Stress Conic 72

3.3.2 The Shear Stress Quartic 73

3.3.3 The Stress Ellipse 74

3.4 Symmetry of the Surface Stress: Eccentricity and Orientation 75

3.4.1 Stereography and Surface Stress 77

3.4.2 Racemic Surface Stress 79

3.4.3 Adsorbate-Induced Asymmetry in Surface Stress 80

3.5 Measurement of Differential Surface Stress 81

3.5.1 Island Shape Measurement 81

3.5.2 Contact Angle Measurement 82

3.5.3 Cantilever Deformation 85

3.6 Facet Formation and theWulff Construction 86

3.6.1 Ridge-and-Furrow Facets 86

3.6.2 Pyramid-and-Pit Facets 88

3.6.3 Geometrical Construction 89

References 91

4 Asymmetric Adsorption on Achiral Substrates 93

4.1 Achiral Adsorbates: GlidingThrough Broken Mirrors 93

4.2 Prochiral Adsorbates: Chirality in Context 97

4.2.1 Guanine on Au{111} 98

4.2.2 Stilbene Derivatives on Cu{100} and Cu{110} 101

4.2.3 Glycine on Cu{110} and Cu{311} 102

4.2.4 Succinic and Fumaric Acids on Cu{110} 107

4.2.5 Meso-Tartaric Acid on Cu{110} 111

4.3 Chiral Adsorbates: Act Locally,Think Globally 112

4.3.1 Alanine on Cu{110} and Cu{311} 112

4.3.2 Proline on Cu{110} and Cu{311} 120

4.3.3 Serine and Lysine on Cu{110} 125

4.3.4 Cysteine on Cu{110} and Au{110} 128

4.3.5 Tartaric Acid on Cu{110} 135

4.3.6 Glutamic Acid on Ag{110} and Ag{100} 140

4.3.7 2-Butanol on Au{111} 145

4.3.8 Tartaric Acid on Ni{111} 146

4.3.9 Alanine on Pd{111} 147

4.4 Chiral Facetting: Remodelling the Surface 149

4.4.1 Glycine, Alanine and Lysine on Cu{100} 150

4.5 Chiral Metallorganic Frameworks: Into the Second Dimension 151

4.5.1 Glutamic Acid on Ni/Au{111} 152

4.5.2 Lysine on Ni/Au{111} 153

4.5.3 Proline on Ni/Au{111} 154

4.6 Executive Summary 156 Refe...